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Two closely related isomeric pairs of cyanides, CH3[CN/NC] and H2C[CN/NC], are studied in cold, dark interstellar cloud conditions. In contrast to the diverse detections of methyl cyanide (CH3CN) in space, methyl isocyanide (CH3NC) has previously only been observed in warm and hot star-forming regions. We report the detection of CH3NC in the cold pre-stellar core Taurus Molecular Cloud (TMC-1) using the Green Bank Telescope with a detection significance of 13.4σ. Hyperfine transitions in H2CCN and quadrupole interactions in CH3CN and CH3NC were matched to a spectral line survey from the Green Bank Telescope Observations of TMC-1: Hunting for Aromatic Molecules large project on the Green Bank Telescope, resulting in abundances with respect to hydrogen of |$1.92^{+0.13}_{-0.07} \times 10^{-9}$| for the cyanomethyl radical (H2CCN), |$5.02^{+3.08}_{-2.06} \times 10^{-10}$| for CH3CN, and |$2.97^{+2.10}_{-1.37} \times 10^{-11}$| for CH3NC. Efforts to model these molecules with the three-phase gas-grain code nautilus in TMC-1 conditions overproduce both CH3CN and CH3NC, though the ratio of ∼5.9 per cent is consistent across observations and models of these species. This may point to missing destruction routes in the model. The models capture the larger abundance of H2CCN well. Dissociative recombination is found to be the primary production route for these molecules, and reactions with abundant ions are found to be the primary destruction routes. H + CH3NC is investigated with transition state theory as a potential destruction route, but found to be too slow in cold cloud conditions to account for the discrepancy in modelled and observed abundances of CH3NC. [ABSTRACT FROM AUTHOR]

Context. A lower-than-solar elemental nitrogen content has been demonstrated for several comets, including 1P/Halley and 67P/Churyumov-Gerasimenko (67P/C-G) with independent in situ measurements of volatile and refractory budgets. The recently discovered semi-refractory ammonium salts in 67P/C-G are thought to be the missing nitrogen reservoir in comets. Aims. The thermal desorption of ammonium salts from cometary dust particles leads to their decomposition into ammonia (NH3) and a corresponding acid. The NH3/H2O ratio is expected to increase with decreasing heliocentric distance with evidence for this in near-infrared observations. NH3 has been claimed to be more extended than expected for a nuclear source. Here, the aim is to constrain the NH3/H2O ratio in comet C/2020 F3 (NEOWISE) during its July 2020 passage. Methods. OH emission from comet C/2020 F3 (NEOWISE) was monitored for 2 months with the Nançay Radio Telescope (NRT) and observed from the Green Bank Telescope (GBT) on 24 July and 11 August 2020. Contemporaneously with the 24 July 2020 OH observations, the NH3 hyperfine lines were targeted with GBT. From the data, the OH and NH3 production rates were derived directly, and the H2O production rate was derived indirectly from the OH. Results. The concurrent GBT and NRT observations allowed the OH quenching radius to be determined at (5.96 ± 0.10) × 104 km on 24 July 2020, which is important for accurately deriving Q(OH). C/2020 F3 (NEOWISE) was a highly active comet with Q(H2O) ≈ 2 × 1030 mol s−1 one day before perihelion. The 3σ upper limit for QNH3 / QH2O is < 0.29% at 0.7 au from the Sun. Conclusions. The obtained NH3/H2O ratio is a factor of a few lower than measurements for other comets at such heliocentric distances. The abundance of NH3 may vary strongly with time depending on the amount of water-poor dust in the coma. Lifted dust can be heated, fragmented, and super-heated; whereby, ammonium salts, if present, can rapidly thermally disintegrate and modify the NH3/H2O ratio. [ABSTRACT FROM AUTHOR]

Single-dish observations at centimeter wavelengths have suggested that the Sgr B2 molecular cloud at the Galactic Center hosts weak maser emission from several large molecules. Here, we present the interferometric observations of the Class I methanol (CH3OH) maser at 84 GHz, the methanimine (CH2NH) maser at 5.29 GHz, and the methylamine (CH2NH2) maser at 4.36 GHz toward Sgr B2 North (N). We use a Bayesian approach to quantitatively assess the observed masing spectral profiles and the excitation conditions. By comparing the spatial origin and extent of maser emission from several molecular species, we find that the new maser transitions have a close spatial relationship with the Class I masers, which suggests a similar collisional pumping mechanism. [ABSTRACT FROM AUTHOR]

Owing to its unparalleled structural specificity, rotational spectroscopy is a powerful technique to unambiguously identify and characterize volatile, polar molecules. We present here a new experimental approach, automated microwave double resonance (AMDOR) spectroscopy, to rapidly determine the rotational constants of these compounds without a priori knowledge of elemental composition or molecular structure. This task is achieved by rapidly acquiring the classical (frequency vs. intensity) broadband spectrum of a molecule using chirped-pulse Fourier transform microwave (FTMW) spectroscopy and subsequently analyzing it in near real-time using complementary cavity FTMW detection and double resonance. AMDOR measurements provide a unique "barcode" for each compound from which rotational constants can be extracted. To illustrate the power of this approach, AMDOR spectra of three aroma compounds - trans-cinnamaldehyde, α-, and β-ionone - have been recorded and analyzed. The prospects to extend this approach to mixture characterization and purity assessment are described. [ABSTRACT FROM AUTHOR]

HOCO is an important intermediate in combustion and atmospheric processes because the OH + CO → H + CO2 reaction represents the final step for the production of CO2 in hydrocarbon oxidation, and theoretical studies predict that this reaction proceeds via various intermediates, the most important being this radical. Isotopic investigations of trans- and cis-HOCO have been undertaken using Fourier transform microwave spectroscopy and millimeter-wave double resonance techniques in combination with a supersonic molecular beam discharge source to better understand the formation, chemical bonding, and molecular structures of this radical pair. We find that trans- HOCO can be produced almost equally well from either OH + CO or H + CO2 in our discharge source, but cis-HOCO appears to be roughly two times more abundant when starting from H + CO2. Using isotopically labelled precursors, the OH + C18O reaction predominately yields HOC18O for both isomers, but H18OCO is observed as well, typically at the level of 10%-20% that of HOC18O; the opposite propensity is found for the 18OH + CO reaction. DO + C18O yields similar ratios between DOC18O and D18OCO as those found for OH + C18O, suggesting that some fraction of HOCO (or DOCO) may be formed from the back-reaction H + CO2, which, at the high pressure of our gas expansion, can readily occur. The large 13C Fermi-contact term (aF) for trans- and cis-HO13CO implicates significant unpaired electronic density in a σ-type orbital at the carbon atom, in good agreement with theoretical predictions. By correcting the experimental rotational constants for zero-point vibration motion calculated theoretically using second-order vibrational perturbation theory, precise geometrical structures have been derived for both isomers. [ABSTRACT FROM AUTHOR]

The nuclear spin dependence of the chemical reaction H3++ H2 → H2 + H3+ has been studied in a hollow cathode plasma cell. Multipass infrared direct absorption spectroscopy has been employed to monitor the populations of several low-energy rotational levels of ortho- and para-H3+ (o-H3+ and p-H3+) in hydrogenic plasmas of varying para-H2 (p-H2) enrichment. The ratio of the rates of the proton hop (kH) and hydrogen exchange (kE) reactions α ≡ kH/kE is inferred from the observed p-H3+ fraction as a function of p-H2 fraction using steady-state chemical models. Measurements have been performed both in uncooled (Tkin ∼ 350 K) and in liquid-nitrogen-cooled (Tkin ∼ 135 K) plasmas, marking the first time this reaction has been studied at low temperature. The value of α has been found to decrease from 1.6 ± 0.1 at 350 K to 0.5 ± 0.1 at 135 K. [ABSTRACT FROM AUTHOR]

We report the gas-phase detection and spectroscopic characterisation of ethynethiol (), a metastable isomer of thioketene () using a combination of Fourier-transform microwave and submillimetre-wave spectroscopies. Several a-type transitions of the normal species were initially detected below 40 GHz using a supersonic expansion-electrical discharge source, and subsequent measurement of higher-frequency, b-type lines using double resonance provided accurate predictions in the submillimetre region. With these, searches using a millimetre-wave absorption spectrometer equipped with a radio frequency discharge source were conducted in the range 280–660 GHz, ultimately yielding nearly 100 transitions up to and. From the combined data set, all three rotational constants and centrifugal distortion terms up to the sextic order were determined to high accuracy, providing a reliable set of frequency predictions to the lower end of the THz band. Isotopic substitution has enabled both a determination of the molecular structure of HCCSH and, by inference, its formation pathway in our nozzle discharge source via the bimolecular radical-radical recombination reaction , which is calculated to be highly exothermic (−477 kJ/mol) using the HEAT345(Q) thermochemical scheme. [ABSTRACT FROM AUTHOR]

Context. In the search for the building blocks of life, nitrogen-bearing molecules are of particular interest since nitrogen-containing bonds are essential for the linking of amino acids and ultimately the formation of larger biological structures. The elusive molecule methylamine (CH3NH2) is thought to be a key pre-biotic species but has so far only been securely detected in the giant molecular cloud Sagittarius B2. Aims. We identify CH3NH2 and other simple nitrogen-bearing species involved in the synthesis of biologically relevant molecules towards three hot cores associated with the high-mass star-forming region NGC 6334I, located at a distance of 1.3 kpc. Column density ratios are derived in order to investigate the relevance of the individual species as precursors of biotic molecules. Methods. High sensitivity, high angular and spectral resolution observations obtained with the Atacama Large Millimeter/ submillimeter Array were used to study transitions of CH3NH2, CH2NH, NH2CHO, and the 13C- and 15N-methyl cyanide (CH3CN) isotopologues, detected towards NGC 6334I. Column densities are derived for each species assuming local thermodynamic equilibrium and excitation temperatures in the range 220–340 K for CH3NH2, 70–110 K for the CH3CN isotopologues and 120–215 K for NH2CHO and CH2NH. Results. We report the first detections of CH3NH2 towards NGC 6334I with column density ratios with respect to CH3OH of 5.9 × 10−3, 1.5 × 10−3 and 5.4 × 10−4 for the three hot cores MM1, MM2, and MM3, respectively. These values are slightly lower than the values derived for Sagittarius B2 but higher by more than an order of magnitude as compared with the values derived for the low-mass protostar IRAS 16293–2422B. The column density ratios of NH2CHO, 13CH3CN, and CH3C15N with respect to CH3OH are (1.5 – 1.9) × 10−4, (1.0 – 4.6) × 10−3 and (1.7 – 3.0) × 10−3 respectively. Lower limits of 5.2, 1.2, and 3.0 are reported for the CH3NH2 to CH2NH column density ratio for MM1, MM2, and MM3 respectively. These limits are largely consistent with the values derived for Sagittarius B2 and higher than those for IRAS 16293–2422B. Conclusions. The detections of CH3NH2 in the hot cores of NGC 6334I hint that CH3NH2 is generally common in the interstellar medium, albeit that high-sensitivity observations are essential forthe detection of the species. The good agreement between model predictions of CH3NH2 ratios and the observations towards NGC 6334I indicate a main formation pathway via radical recombination on grain surfaces. This process may be stimulated further by high grain temperatures allowing a lager degree of radical mobility. Further observations with ALMA will help evaluate the degree to which CH3NH2 chemistry depends on the temperature of the grains in high- and low-mass star-forming regions respectively. [ABSTRACT FROM AUTHOR]

The recent astronomical detection of benzonitrile (C6H5CN) in the cold, starless cloud TMC-1 demonstrates that aromatic chemistry is efficient even in the primordial stages of star and planet formation. C6H5CN may serve as a convenient observational proxy for benzene, which is otherwise challenging to detect in space, provided the chemistry linking these two molecules is tightly constrained. Here we present a high-resolution microwave spectroscopic study in combination with an accurate thermochemical treatment of the formation chemistry of C6H5CN and benzene. We demonstrate that C6H5CN is a highly useful tracer for benzene in the presence of CN radical, either in space or in the laboratory, and by inference, that the reaction C2H + CH2(CH)2CH2 yields benzene, along with its high-energy polar isomer fulvene. In addition, we find that the higher energy isomer, C6H5NC, is formed at ＜0.1% abundance relative to C6H5CN. By exploiting –CN tagging, formation pathways to produce benzene using a variety of acyclic hydrocarbon precursors are then explored. A robust, self-consistent, and chemically accurate theoretical treatment has also been undertaken for several key reactions. The results are discussed both in the context of aromatic molecule synthesis and astrochemistry. [ABSTRACT FROM AUTHOR]

We present a microwave spectral taxonomy study of several hydrocarbon/CS2 discharge mixtures in which more than 60 distinct chemical species, their more abundant isotopic species, and/or their vibrationally excited states were detected using chirped-pulse and cavity Fourier-transform microwave spectroscopies. Taken together, in excess of 85 unique variants were detected, including several new isotopic species and more than 25 new vibrationally excited states of C2S, C3S, and C4S, which have been assigned on the basis of published vibration–rotation interaction constants for C3S, or newly calculated ones for C2S and C4S. On the basis of these precise, low-frequency measurements, several vibrationally exited states of C2S and C3S were subsequently identified in archival millimeter-wave data in the 253–280 GHz frequency range, ultimately providing highly accurate catalogs for astronomical searches. As part of this work, formation pathways of the two smaller carbon–sulfur chains were investigated using 13C isotopic spectroscopy, as was their vibrational excitation. The present study illustrates the utility of microwave spectral taxonomy as a tool for complex mixture analysis, and as a powerful and convenient ‘stepping stone’ to higher frequency measurements in the millimeter and submillimeter bands. [ABSTRACT FROM AUTHOR]

Bell et al. reported the first detection of the cyanopolyyne HC11N towards the cold dark cloud TMC-1; no subsequent detections have been reported towards any source. Additional observations of cyanopolyynes and other carbon-chain molecules towards TMC-1 have shown a log-linear trend between molecule size and column density, and in an effort to further explore the underlying chemical processes driving this trend, we have analysed Green Bank Telescope observations of HC9N and HC11N towards TMC-1. Although we find an HC9N column density consistent with previous values, HC11N is not detected and we derive an upper limit column density significantly below that reported in Bell et al. Using a state-of-the-art chemical model, we have investigated possible explanations of non-linearity in the column density trend. Despite updating the chemical model to better account for ion-dipole interactions, we are not able to explain the non-detection of HC11N, and we interpret this as evidence of previously unknown carbon-chain chemistry. We propose that cyclization reactions may be responsible for the depleted HC11N abundance, and that products of these cyclization reactions should be investigated as candidate interstellar molecules. [ABSTRACT FROM AUTHOR]

The rotational spectra of thioisocyanic acid (HNCS), and its three energetic isomers (HSCN, HCNS, and HSNC) have been observed at high spectral resolution by a combination of chirped-pulse and Fabry–Pérot Fourier-transform microwave spectroscopy between 6 and 40 GHz in a pulsed-jet discharge expansion. Two isomers, thiofulminic acid (HCNS) and isothiofulminic acid (HSNC), calculated here to be 35–37 kcal mol−1 less stable than the ground state isomer HNCS, have been detected for the first time. Precise rotational, centrifugal distortion, and nitrogen hyperfine coupling constants have been determined for the normal and rare isotopic species of both molecules; all are in good agreement with theoretical predictions obtained at the coupled cluster level of theory. On the basis of isotopic spectroscopy, precise molecular structures have been derived for all four isomers by correcting experimental rotational constants for the effects of rotation–vibration interaction calculated theoretically. Formation and isomerization pathways have also been investigated; the high abundance of HSCN relative to ground state HNCS, and the detection of strong lines of SH using CH3CN and H2S, suggest that HSCN is preferentially produced by the radical–radical reaction HS + CN. A radio astronomical search for HSCN and its isomers has been undertaken toward the high-mass star-forming region Sgr B2(N) in the Galactic Center with the 100 m Green Bank Telescope. While we find clear evidence for HSCN, only a tentative detection of HNCS is proposed, and there is no indication of HCNS or HSNC at the same rms noise level. HSCN, and tentatively HNCS, displays clear deviations from a single-excitation temperature model, suggesting weak masing may be occurring in some transitions in this source. [ABSTRACT FROM AUTHOR]

The icy mantles of interstellar dust grains are the birthplaces of the primordial prebiotic molecular inventory that may eventually seed nascent solar systems and the planets and planetesimals that form therein. Here, we present a study of two of the most abundant species in these ices after water: carbon dioxide (CO2) and methanol (CH3OH), using TeraHertz (THz) time-domain spectroscopy and mid-infrared spectroscopy. We study pure and mixed-ices of these species, and demonstrate the power of the THz region of the spectrum to elucidate the long-range structure (i.e. crystalline versus amorphous) of the ice, the degree of segregation of these species within the ice, and the thermal history of the species within the ice. Finally, we comment on the utility of the THz transitions arising from these ices for use in astronomical observations of interstellar ices. [ABSTRACT FROM AUTHOR]

Life on Earth relies on chiral molecules--that is, species not superimposable on their mirror images. This manifests itself in the selection of a singlemolecular handedness, or homochirality, across the biosphere. We present the astronomical detection of a chiral molecule, propylene oxide (CH3CHCH2O), in absorption toward the Galactic center. Propylene oxide is detected in the gas phase in a cold, extended molecular shell around the embedded, massive protostellar clusters in the Sagittarius B2 star-forming region. This material is representative of the earliest stage of solar system evolution in which a chiral molecule has been found. [ABSTRACT FROM AUTHOR]

Presented here is a set of demonstrations that are used as visual tools for engaging students in a discussion of reaction chemistry and thermodynamics. Students are first shown a series of simple exothermic reactions: (1) the reaction of H2SO4 with sugar, (2) the decomposition of KClO3, and (3) the reaction of H2SO4 with KClO3. These three basic reactions are then combined as a pyrotechnic chlorate demonstration in which H2SO4 is used to ignite a KClO3 + sugar mixture. It is finally shown that this latter reaction is very effective for igniting the highly exothermic thermite redox reaction. [ABSTRACT FROM AUTHOR]

The results of a Caltech Submillimeter Observatory (CSO) search for l-C3H+, first detected by Pety et al. in observations towards the Horsehead photodissociation region (PDR), are presented. A total of 39 sources were observed in the 1 mm window. Evidence of emission from l-C3H+ is found in only a single source – the Orion Bar PDR region – which shows a rotational temperature of 178(13) K and a column density of 7(2) × 1011 cm−2. In the remaining sources, upper limits of ∼1011–1013 cm−2 are found. These results are discussed in the context of guiding future observational searches for this species. [ABSTRACT FROM PUBLISHER]

Icy dust grains play a key role in the chemistry of the interstellar medium. The cumulative outcome of recent observations, laboratory studies, and astrochemical models indicates that solid-phase reaction mechanisms may dominate the formation of complex organic molecules such as amino acids and sugars in space. Consequently, the composition and structure of the icy grain mantle may significantly influence solid-phase reaction pathways. In this work, we present a new experimental setup capable of studying astrochemical ice analogs in both the TeraHertz (THz), or far-Infrared (far-IR), region (0.3–7.5 THz; 10–250 cm−1) and the mid-IR (400–4000 cm−1). The instruments are capable of performing a variety of spectroscopic studies that can provide especially relevant laboratory data to support astronomical observations from telescopes such as Herschel, SOFIA, and ALMA. Experimental spectra of astrochemical ice analogs of water and carbon dioxide in pure, mixed, and layered ices were collected at different temperatures under high vacuum conditions with the goal of investigating the structure of the ice. We tentatively observe a new feature in both amorphous solid water and crystalline water at 33 cm−1 (1 THz). In addition, our studies of mixed and layered ices show how it is possible to identify the location of carbon dioxide as it segregates within the ice by observing its effect on the THz spectrum of water ice. The THz spectra of mixed and layered ices are further analyzed by fitting their spectral features to those of pure amorphous solid water and crystalline water ice to quantify the effects of temperature changes on structure. From the results of this work, it appears that THz spectroscopy is potentially well suited to study thermal transformations within the ice. [ABSTRACT FROM AUTHOR]

The article focuses on the mirror asymmetry both in space and in life. Topics discussed include the origin of the mirror asymmetry in life and space, the evolution of living organisms with amino acid as the primary component, the possible destruction of enantiomer, and the generation of enantiomeric excess.